PL128453B1 - Fuel additive - Google Patents

Description

The subject of the invention is an additive for fuels. There are known additives to fuel oil, obtained by distillation, which are added to facilitate the flow of wax-containing metallic fuels through pipelines and filters at low temperature. British Patent Nos. 900 202 and 1263 152 disclose the use of low molecular weight copolymers of ethylene and unsaturated esters, especially vinyl acetate, for this purpose, while British Patent No. 1,374,051 discusses the use of an additive system which increases the temperature to initiate wax crystallization and also limits the size of the wax crystals. The use of ethylene copolymers and other low molecular weight olefins as liquid temperature depressants of distillate fuels is described in British Patent Nos. 848,777, 993,744 and 10C8000 and US Pat. US Am. No. 3,679,380. It has also been proposed to facilitate the flow and to improve the fluidity properties of fuels obtained by distillation using an additive blend. For example, US Patent No. 3,661,541 discloses the use of an additive blend of the ethylene copolymer type. and unsaturated ester, and the low molecular weight ethylene / propylene copolymers prepared according to British Patent No. 993,774, contain small amounts of propylene. US Patent No. 3,658 498 discusses the use of various nitrogen salts and acid amides, such as acids, mono- and dicarboxylic acids, phenols, and sulfonic acids, in combination with polymeric or copolymeric ethylene depressants for medium oils obtained by distillation. US No. 3,982,909 discusses the use of nitrogen-containing compounds such as amides, diamides, and ammonium mono-amides or monoesters. dibycarboxylic acids alone or in combination with a microcrystalline petroleum wax and / or a liquid temperature depressant, being as wax crystal modifiers and low temperature flow improvers for the diameters of distillated oil fuels, especially for pellets for high-pressure similics, polymeric liquid temperature depressants, hexagonal with an ethylene backbone, are used. US Am. Nos. 3,444,082 and 3,94G693 discuss the use of amides and amine salts of alkenyl succinic anhydride in conjunction with an ethylene copolymer-type depressant for distillate fuels. 128 453128 453 The above-described additives are used to lower the liquid temperature of the fuels obtained by distillation, preventing the oil from gelling through the formation of wax crystals and / or by reducing their size, to facilitate the flow of wax-containing oils through filters. Although the achievement of the above effects is important when further reducing the size of the wax crystals, there is an additional problem with oils with improved flow temperature and flow characteristics, namely when the oil is stored at low temperature, the wax crystals form tend to form Due to the large volume of oil stored in the tanks, the temperature of the oil mass drops slowly even when the ambient temperature is well below the oil melting point (the temperature at which the wax becomes It starts to crystallize and becomes visible, ie the oil becomes cloudy). In particularly cold and long winters, when the oil is stored at low temperatures for a long time, its temperature, even in large commercial tanks, can drop below the melting point. Such conditions can cause wax agglomeration, which increases continuously as the higher density wax accumulates in the lower part of the tank. It has been found that these difficulties can be significantly reduced by using certain mixtures of additives. It has also been found that under certain conditions, the use of these of the additive mixtures, it is possible to counteract the crystal growth better than by using a similar concentration of the previously described additives. The fuel additive according to the invention comprises a copolymer of 4-20 mole parts of ethylene and 1 part of an unsaturated ester of the general formula RiRfC = CHHg, in which Ri is the methyl group. or a hydrogen atom, R * represents a group of the formula -hCOOR4 or -OOCR4, in which the formulas R 'represents an alkyl group of 1-28 carbon atoms and Rt represents a hydrogen atom or a group of the formula---COOR * and an ethylene copolymer and propylene or isobutylene with a molecular weight of 10,000-100,000. The feature of the additive according to the invention is that it contains an oil-soluble nitrogen compound with a total a group of carbon atoms of 30-300, having at least one straight-chain alkyl segment of 8-40 carbon atoms and being the salt of the amine and / or the hydrocarbyl amide of a carbonyl acid or its anhydride with 1-4 carbonyl groups, calculated from for 1 part by weight of ethylene-ester copolymer the mixture contains 0.1-10 parts by weight of ethylene-propylene or isobutylene copolymer and 0.1-10 parts by weight of an oil-soluble nitrogen compound. The nitrogen-containing compound is preferably a derivative of phthalic acid or phthalic anhydride, in which both carboxyl groups are reacted with the secondary alkyl monoamide containing alkyl groups essentially of 14-18 carbon atoms. It has been found that the additives according to the invention are of particular use for oil fuels obtained by distillation, the temperature of which is boiling point is 120-500 ° C, especially 160-400 ° C, 5 in order to counteract the growth and agglomeration of the secreted waxes. In the following, the blend components are abbreviated as Class A substances (ethylene-unsaturated ester copolymer), Class B substances (ethylene-propylene or isobutylene copolymer and Class C substances (nitrogen compound). is 0.01-1.0% by weight, preferably 0.001-0.5% by weight, for example 0.005-0.2% by weight, and even more preferably 0.01-0.2% by weight and most preferably 0.005-0.05% by weight, for example 0.02-0.1% by weight. In the mixture, the ratio of substances from classes A, B and C, expressed in parts by weight, is 0.1-10. Preferably, the additive mixture comprises 1 part by weight of a substance of class A, 0.1-10, preferably 0.2-2 parts by weight of a substance of class B, and 0.1-10, preferably 0.2-1 part by weight of a polar nitrogen compound soluble in of oil 25 (substance of class C). For easier handling, the mixtures can be formulated as concentrates containing 10-90% by weight, preferably 30-80% by weight, of a hydrocarbon solvent. The class A distillate flow-enhancing substance which is used in the additive blend of the invention is a wax crystal growth-inhibiting substance, which may also contain a wax-crystal nucleating substance, as described in British Patent Specification No. 1,374,051. Such crystal growth inhibitors and nucleating agents are preferably ethylene polymers of the type known in the art as wax crystal modifiers, for example liquid temperature depressants and low temperature flow improvers of the oil fuels obtained by the route. distillation. Such polymers contain a polymethylene main chain segmented by oxyhydrocarbyl side chains. They may be ethylene polymers which are produced by free radical polymerization, which may give rise to some amount of branches. More commonly they are copolymers consisting of ethylene and another ethylenically unsaturated monomer in a molar ratio of 3:40, preferably 4:20, the unsaturated ethylen polymer being defined below. It may be a single monometer or a mixture of monomers in any proportion. The polymers usually have a number average molecular weight of 500-50,000, e.g., 500-10,000, preferably 1,000-6,000, as measured by membraneless osmometry. 60 Unsaturated monomers copolymerizable with ethylene include unsaturated mono- and diesters of formula R1R1C = CHR8, in which Ri is hydrogen or a methyl group, Ra is a group of formula —OOCR4, in which R4 is straight or branched alkyl group with 1-28,128,453 carbon atoms, more often 1-17, and preferably 1-8 carbon atoms, or Rj is a group of formula -COOR4, where R4 is as defined above and Rj is hydrogen or formula COOR4 as defined above. The monomers in which Rt and R8 are hydrogen and Ra is the group —OOCR4 include esters of vinyl alcohol with 1-29 carbon atoms, more often 1-18 carbon atoms, monocarboxylic acid, and preferably 2— monocarboxylic acid. 5 carbon atoms. Examples of such esters are vinyl acetate, vinyl isobutyrate, vinyl laurate, vinyl myristate and vinyl palmitate, with vinyl acetate being the preferred ester. When R2 is COOR4 and Rj is hydrogen, such esters include methyl acrylate, isobutyl acrylate, methyl methacrylate, lauryl acrylate, oxyalkoxy esters of 13 carbon atoms and methacrylic acid, etc. monomers in which R 1 is hydrogen and Rj and R are groups of the formula —COOR 4, are diesters of unsaturated dicarboxylic acids, such as monooxyfurate with 13 carbon atoms, dioxifuarate with 13 carbon atoms, diisopropropyl maleate Dust, binaryyl fumarate, and ethylmethyl fumarate. Preferred ethylene copolymers are those of ethylene with vinyl esters, particularly vinyl acetate. Such copolymers can be made using elevated pressure, with or without a solvent. When the copolymerization is carried out in solution, the solvent and 5 to 50% by weight of the total amount of the non-ethylene monomer introduced are introduced into a stainless steel pressure vessel equipped with an agitator and a heat exchanger. The temperature of the pressure vessel is then increased to the required reaction temperature, e.g. 70 ° C to 200 ° C, while at the same time the pressure in the ethylene autoclave is increased to the required pressure, e.g., 4.83 to 172.5 MPa, typically 6.21-8.3 MPa. The initiator, usually racemic (or dissolved when solid) in the polymerization solvent is injected during polymerization, and additional amounts of non-ethylene monomer, such as vinyl ester, are injected into the vessel continuously, or at least intermittently, throughout the reaction. Also during the course of the reaction, as ethylene is consumed in the polymerization reaction, an additional amount of it is supplied through the pressure regulator so as to maintain the required reaction pressure at a clearly constant value at all times. The co-polymerization temperature is kept virtually constant by means of a heat exchanger. After the reaction is complete (usually the total reaction time is 0.25-10 hours), the liquid phase is removed from the reactor. After removal of the solvent and other volatile constituents, the copolymer remains as residue. For ease of use and blending, the copolymer is generally dissolved in mineral oil and preferably in an aromatic solvent such as aromatic naphtha to form a concentrate usually containing 10-60% by weight of a copolymer. The initiator belongs to the class of compounds such as peroxide or nitrogen-type initiators, which include simple or branched acyl peroxides containing 2-18 carbon atoms, carboxylic acids, and other common initiators which decompose at 5 elevated temperatures with the formation of radicals. Typical examples of such initiators are diberaoyl peroxide, tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl percaprylate, 10 n-butyl hydroperoxide, a- , α-diisobutyronitrile, dularoyl peroxide, etc. The choice of peroxide is made taking into account the primary polymerization conditions used, the required polymer structure and the initiator efficiency. Preferred initiators are H1-tert-butyl peroxide, dulauroyl peroxide and di-tertiary-butyl peroxide. A high molecular weight, oil-soluble class B substance, preferably an olefinic copolymer, has a numerical average weight. molecular weight in the range 10-105, most preferably 10,000-50,000 (determined by gel chromatography or more preferably membrane osmometry). The class B hydrocarbon polymers used in the blend of the invention are ethylene copolymers containing 15-90% by weight of ethylene, preferably 30-80% by weight and 10-85% by weight, preferably 20-70% by weight of another alpha-olefin, i.e. propylene or isobutylene. However, it is irrelevant that such copolymers preferably have a degree of crystallization of less than 25% by weight (determined by X-ray and differential layer spectrophotometry). Ethylene-propylene copolymers are most preferred. Ethylene copolymers can be prepared using well known methods. Ziegler-Natta catalyst blends as described in British Patent Specification No. 1,397,995. Such polymerization into an ethylene copolymer can be carried out with 0.1-15, for example, 5 parts of ethylene, 0.05-10, e.g. 2.5 parts of said higher α-olefin, e.g. propylene, and 10-10,000 parts of hydrogen per million parts of ethylene, to 100 parts of an inert liquid solvent containing about 0.0017-0.017, e.g., 0.0086 parts of the primary catalyst of the transition metal type, e.g. COCI8 and about 0.0084 ^ -0.084, e.g. 0.042 parts of the catalyst, e.g. (C2H5) | A12C13, at a temperature of about 25 ° C and a pressure of about 414 kPa for sufficient time to optimum conversion is obtained, for example, 15 minutes - 1.5 hours. The above-mentioned parts are parts by weight. Particularly effective oil-soluble polar compounds for keeping the wax crystals separate from each other, i.e. compounds containing nitrogen, i.e. substances of the class C of the additive mixtures according to the invention, to inhibit agglomeration of the wax crystals. Examples of suitable compounds are the amine salts and / or amides, which are usually prepared by reacting at least one mole portion of the amine with one mole portion of a hydrocarbon acid containing 1-4 acidic carboxyl groups or their anhydrides. 357 In the case of polycarboxylic acids or their anhydrides, all acid groups may be converted to amine salts, or amides, or several acid groups may be converted to esters by reaction with hydrocarbon alcohols or may remain unreacted. Examples of suitable amides are "succinic acid amides" as given in British Patent Specification No. 1,140,771. The hydrocarbyl groups of the nitrogen containing compounds described above may be straight or branched chain, saturated or unsaturated, aliphatic, cycloaliphatic, aryl or alkylaryl groups. and long carbon lances, e.g. 12 to 40, preferably 14 to 24, carbon atoms. However, it is also possible to use compounds with groups having shorter carbon chains, e.g. 1 to 11 carbon atoms, assuming that the total number of carbon atoms in the The compound allows it to be soluble in oil obtained by distillation. Usually, a total carbon number of 30-300, e.g. 36-160, allows solubility in the oil, although the required number of carbon atoms varies depending on the degree of polarity of the compound. A Class C compound also contains at least one straight chain alkyl segment of 8-40, preferably 12-30 carbon atoms. This straight chain alkyl segment may be in one or more amine groups or ammonium ions, in acid groups or in an alcohol group (if an ester group is also present). It is required that at least one amine salt or amide linkage be present in the molecule. Hydrocarbon groups may contain other groups or atoms such as hydroxyl groups, catibonyl groups, esters or oxygen, sulfur or chlorine atoms. reactions with cartoxylic acids include primary, secondary, tertiary or quaternary amines, but are preferably secondary amines. If amides are to be formed, secondary or secondary amines are used. Examples of primary amines are n-dodecylamine, n-tridecylamine, tridecanoxyamine, cocoimna, fatty amine, and benzylamine. Examples of drug-derived amines are methyllaurylamine, dodecylphthylamine, cocomethylamine, methyl-n-octylamine, methyl-n-octylamine, methyl-n-dodecylamine, methylbhenylamine, and double-hydrogenated fatty amine. - Methylamine, cyclohexyldiethylamine, cocodimethylamine and methylcetyl stearylamine, methyl ethylcocamine, methylcetyl stearylamine, etc. Examples of quaternary amines are ammonium cations or salts such as dimethyl-dimethylamino chloride and dimethyldimethylamine with many mixtures of aminosylamine as well as mixed aminosylamine. natural substances are mixtures thereof. Thus, cocoamines obtained from coconut oil are a mixture of? 453? 8 primary amines with alkyl groups containing straight carbon chains of 8-18 carbon atoms. (Another example is a hydrogenated fatty amine derived from fatty acids, the amine containing a mixture of straight carbon chain alkyl groups of 14-18 carbon atoms. Hydrogenated fatty amine is particularly preferred. An example of the carboxylic acid or anhydride is an acid. formic, acetic, hexanoic, lauric, myristic, palmitic, hydroxystearic, behenic, naphthenic, salicylic, linoleic, dimolic, trilinoleic, maleic, maleic anhydride, fumaric acid, succinic, anhydride described above, succinic, alkenyl succinic water, adipic, glutaric, sebacic, lactic, malonic, malonic, citraconic, phthalic acids (ortho, meta or 20 Para) ^ P-terephthalic, phthalic anhydride, citric acid, gluconic, tartaric acid, 9,10-dihydrate - systearic and cyclohexane-1,2-dicarboxylic. Typical examples of alcohols which can react with acids are 1-tetradecanol, oxoalcohols containing e 13-18 carbon atoms which are formed from the mixture of olefins obtained from cracked waxes, 1-hexadecanol, 1-octadecanol, behanyl, 1,2-dihydroxyoctadecane and 1,10-dihydroxydecane. The amides can be prepared by traditional methods by heating a primary or secondary amine with an acid or an acid anhydride. Similarly, an ester is made by traditional methods by heating an alcohol and a polycarboxylic acid to partially esterify the acid or anhydride (so that one or more carboxyl groups remain, which can react with amine to form amides or amine salts). Alkylammonium salts are also prepared by conventional methods by mixing the amine (or ammonium hydroxide) with an acid or acid anhydride, or with a partial polycarboxylic acid ester or partial polycarboxylic acid amide, with stirring, usually by gently heating the reaction mixture (e.g., to 60-80 ° C). C). Nitrogen-containing compounds of the above-mentioned types, which are prepared from dicarboxylic acids, are particularly preferred. Mixtures of amine and amide salts are most preferred, which can be prepared by heating maleic anhydride, alkenyl succinic anhydride, or phthalic acid or anhydride with a secondary amine, preferably a hydrogenated fatty amine, at a mild temperature, for example at 60 ° C. C reduces the size of the wax crystals, which can reduce the rate of wax sedimentation in fuels containing only distillate flow improvers. The presence of the above polar compounds has been found to be of importance under typical fuel storage conditions, even if the fuel is stored for a long time at a low temperature and if its temperature drops very slowly (i.e., about 0.3 ° C / hour). . Oil fuels obtained by distillation, in which the additive mixtures according to the invention are of particular use, have a boiling point of 120-500 ° C, for example 160-400 ° C. The fuel oil may be a distillate obtained under atmospheric pressure, a distillate obtained under reduced pressure, a diesel fuel oil or mixtures thereof obtained in any proportion from the first distillation, and distillates obtained by thermal and / or catalytic cracking. The most popular fuels obtained by distillation of crude oil are kerosene, jet fuels, high-performance fuels and diesel fuels. The diesel fuel may be either a straight run distillate or a cracked fuel oil or a mixture thereof. The low temperature flow difficulties reduced by the use of the additive blends of the invention are most commonly found in diesel fuels and diesel fuels. A recent trend has developed recently. to increase the final boiling point (FBP) of the distillates and thus maximize the fuel efficiency. However, the above fuels are constructed of longer paraffinic chains and therefore usually have higher melting points. This, consequently, increases the difficulty in handling these fuels at low temperatures and increases the need for flow improvers. It has been found that the additive mixture of the invention has a particularly advantageous application with these fuels. The term "oil-soluble" means that the additive dissolves in the fuel * at ambient temperature, e.g. at least 0.1% by weight of the additive in the fuel. oil at 25 ° C, and that at least some of the additive falls out of the solution near the melting point in order to modify the wax crystals formed. The invention is illustrated (the following examples. In the examples, a concentrate in an aromatic solvent is used to improve the distillate flow, containing / about 50% by weight of a mixture of two ethylene vinyl acetate copolymers having different solubilities in oil, with one therefore acting mainly as a crystal growth suppressant and the other as a nucleating agent of crystals according to British Patent Specification No. 1,374,051. More specifically, the substances inhibit the total crystal growth is added in an amount of 75% by weight of the added polymer and the nucleating agent is added in an amount of 25% by weight of the added polymer. The crystal growth inhibitor is composed of ethylene and about 38% by weight of vinyl acetate and has a number average molecular weight of about 1,800 (VPO). It is referred to in the aforementioned British Patent Specification No. 1,374,051 as copolymer B (Example 1, column 8, lines 25-35). The crystal seeding material consists of ethylene and about 16% by weight of vinyl acetate and has a number average molecular weight of 3000 (VPO). It is referred to in the aforementioned British Patent No. 1,374,051 as copolymer H (see table 1, columns 7-8). The distillate flow improver A-2 is a crystal growth suppressant that is a constituent of Al and is used alone. The hydrocarbon polymer BI, which is used as a lubricating oil viscosity index enhancer (V.I), is an ethylene copolymer and a pro Pylene with a number average molecular weight of about 35,000 to 40,000 and determined by membrane osmometry) containing 44% by weight of ethylene, which is substantially linear in structure. It is produced using Ziegler-Natta catalysts. The following polar compounds are used in the examples: Cl - half of the amide and half of the alkyl ammonium salt, which is prepared by reacting - two moles of dihydrogenated fatty amine with one mole of phthalic anhydride, C2 - Diamide which is prepared by dehydrogenation of Cl, C3 - Citric triamide which is produced by dehydrogenation of the product of the reaction of three moles of a dihydrogenated fatty amine with one mole of citric acid. The fuels for which the additives were tested are presented in the table. Table 1 Fuel Melting point, ° C (measured by American standard ASTM JD-2500) Wax appearance temperature, ° C (see American standard ASTM D-3117) Distillation, ° C (American standard ASTM D-86) Initial boiling point ° C 20% boiling point / 90% boiling point Final boiling point | CFPP, ° C (untreated) 1 —3 —6 180 365 —5 2 0 —2 170 372 —1 - 3 C —2 178 238 342 365-2 4-12 200 34 6128 453 11 12 The initial effect of the oil on the additives is measured by the Cold Plugging Temperature Test (CFPPT) which is performed following the procedure detailed in the Journal of the Institute of Petroleum / Vol. 52, No. 510, June. So 1966, pp. 173-185. In short, a 40 ml sample of the oil to be tested is cooled in a bath which is kept at a temperature of approximately -34 ° C. The degreased oil is tested cyclically (for each temperature drop of 1 ° C, starting at least 2 ° C above the melting point) for its ability to flow through a dense sieve in a predetermined period of time. , using a pipette as a tester, to the lower end of which is an inverted funnel placed below the surface of the oil to be tested. A 350 mesh screen with a diameter of 12 mm is stretched on the base of the funnel. Each test is started by applying a vacuum to the upper end of the pipette, the oil being drawn through the screen into the pipette to the mark at 20 ml of oil. Oil is immediately poured into the CFPP tube after each successful attempt. The test is repeated by lowering the oil temperature every 1 ° C until the oil does not fill the pipette within 60 seconds. These temperatures are reported as the CFPP temperature. Another way to define the performance of the additives is to use slower, more natural cooling conditions. The performance of the additives in the described cases is determined by two types of sieve analysis (FSA) under different cooling conditions. FSA1 - 100 g of fuel sample is cooled under special conditions (given below). The obtained samples are shaken to homogenize the wax into the oil suspension. 40 ml of this suspension is poured into a fluid temperature test tube, then a 20 ml pipette with a filter sieve (approximately 1 cm in diameter, mesh size given below) is placed in the tube at the lower end. Wax fuel is then sucked into the pipette (suction pressure is 20 ohm column of water) through a filter sieve. If the pipette fills in less than 30 seconds; the sample is said to pass through the filter sieve, otherwise not. FSA2 - 300 g of the fuel sample is cooled under special conditions (given below). The obtained samples have approximately 20 ml of superficial layers of fuel which are removed by suction to prevent the sample from being influenced by abnormally large wax crystals which tend to form on the surface during cooling. The sample with no crystals on its surface is then shaken to homogenize the wax in the oil suspension. A pipette fitted with a filter sieve similar to that described in the FSA1 test and attached to a 250 ml measuring cylinder is placed in the sample, after which the entire amount of fuel is sucked by pipette into the measuring cylinder through the filter sieve (30 cm column of water under suction pressure). If all the fuel is sucked in in less than 60 seconds, the sample is said to pass through the filter sieve. 20 mesh pipettes with filter sieves are used to determine the smallest mesh size (largest numbers) through which the fuel will pass. , 30, '40, 60, 80, 100, 120, 150, 200, 250, 350 mesh. The method of quenching that is used in the tests is given in Table 2 (letters are used in the examples for okeslemia, which of the quenching methods was used) Table 2 Cooling method STUVWXYZ Cooling rate ° C / hour 1.0 1.0 0.3 1.0 2.5 1.0 0.3 1.0 Initial temperature (° C) 0 0 0 1.5 cycle * 0 0 0 0 cycle * Final temperature (° C) -11.5 -11.5 -11.5 -8.5 -11.5 -11.5 -11.5 '-11.5 Drip off | cold (hours) 36 14 36 9 60 10 22 2 Prófoy marked as cycles are carried out by cooling the fuel from the initial temperature at a rate of 1 ° C / hour to the final temperature, then warming it up at this temperature for 30 hours, heating it to start temperature for 2 hours, keeping at this temperature for 5 hours, then cooling back to the final temperature at 1 ° C / hour. The following examples describe the performance of fuels containing various additives. While all the ingredients can be used as solutions in an inert solvent, all numbers in Examples 1-5 represent the actual concentration of 60 additives per million active ingredient. J5j Example I. The following results shown in Table 3 were obtained, FSA1 flow capacity test. ", Fuel 1.13 128 453 Table 3 14 I Additive (ppm) Flow improver A2 (100) Al (300) A2 (100) Al (100) Al (200) A2 (100) A2 (300) and Al (100) Hydrocarbon polymer BI (100) BI (100) BI (100) BI (100) BI (100) Polar compound / Cl (100) Cl (100) Mesh sizes through which the sample passes * (S) 30 (U) 30 (S) 80 (U) 40 (S) 40 (U) 20 ** (S) 60 (U) 120 (T) 80 (U) 40 (T) 60 (U) 40 (S) 150 (U) 120 (S) 120 (U) 60 (S) 250 (U) 150 CFPP (° C) —6 —19 —10 —16 —20 —16 - 19 —14 —20 • the letters in brackets indicate the method of cooling used ** has not passed Example II. Flow capacity FSA1 flow capacity test Cooling method V. Fuel 1.Table 4 Additive (ppm) Flow improver A2 (207) j A2 (69) A2 (69) A2 (69) Carbon-carbon polymer BI (75) BI (75) BI (75) Polar compound Cl (75) C2 (75) C3 (75) Sizes of the mesh through which the sample passes 30 150 60 60 | 25 30 35 40 Example III. Various hydrocarbon polymers are tested in combination with the flow enhancer A2 and the polar compound C. The hydrocarbon polymer B2 has a number average molecular weight of 60,000-65,000 and contains 44% by weight of ethylene. B3 hydrocarbon polymer has a number average molecular weight of 17,000-20,000. and contains 44% by weight of ethylene. The B4 hydrocarbon polymer has a number average molecular weight of about 55,000 and contains 67% by weight of ethylene. Molecular scales are measured by membrane osmometry and the polymers are produced. using Ziegler-Natta catalysts so that they are essentially linear in structure. FSA1 flow capacity test. Fuel 1. Table 5 \ Additive {ppm) I Substance and flow enhancer 1 "- ~~ ^ ~~~ 'j A2 (125) A2 (250) A2 (175) L A2 (175) A2 (175) A2 (175) 1 A2 (100) X A2 (100) A2 (100) J A2 (100) Hydrocarbon polymer - - B2 (75), BI (75) B3 (75) B4 (75) B2 (50) BI (50) B3 (50) B4 (50) Polar compound - - - - - - Cl (100) Cl (100) Cl (100) Cl (100) )] Size of mesh through which the sample passes re 1 Quenching method IW ¦L 60 120 350 150 150 120 350 350 350 350 X 'o--'%; * £ ¦ 20 40 60 40 40 40 120 60 40 40 Y 1 £ jr * -sag 20 40 60 40 40 40 60 60 40 40 Z 1 350 200 150 | 200 Example IV The way of comparison examines seven hydrocarbon polymers with a lower molecular weight, B5 and B6 in combination with the substance N A2 to improve the flow. The B5 hydrocarbon polymer has a number average molecular weight of about 1500 and contains 89% by weight of ethylene and 11% by weight of propylene and is produced by synthesis. Not free radical B6 hydrocarbon polymer is an ethylene polymer with a number average molecular weight of around 1000 (low density polyethylene) FSA2 flow ability test Cooling method X Fuel 1. Table 6 1 Additive (ppm) Flow improver A2 (100) A2 (125) A2 (150) 1 A2 (100) 1 A2 (100) A2 (100) Polymer hydrocarbon B2 (50) B5 (50) B6 (50) Mesh sizes through which the sample passes 40 40 80 120 | 40 1 40 Example 5 FSA flow capacity test 2 Cooling method X Fuel 3 Table 7 1 Additive (ppm) Flow enhancer A2 (100) A2 (200) A2 (250) A2 (100) A2 (200) Hydrocarbon polymer B2 (100) B2 (50) Passage mesh sizes 40 80 80 80 1 120 This example compares fuels containing flow improvers with fuels containing flow improvers and hydrocarbon polymer. Example VI. The various ethylene propylene copolymers are added to the primary blend of diesel fuel flow improvers and tested in the middle distillate of high pressure fuel oil having a melting point of -12 ° C. The base additive blend (BAP) consists of 20% by weight of a concentrate consisting of 55% by weight of a heavy aromatic kerosene oil and about 45% by weight of the previously described distillate flow improver A2, 20% by weight methyl oil, 10% by weight The C4 polar compound is a diamide which is obtained from one mole of maleic anhydride and two moles of dihydrogenated fatty amine as solvent. The above substances are defined below. Oily fraction - the fine oil fraction used here is obtained as an oil distillation fraction with a boiling point of 370-522 ° C between the lubricating oil fraction and the residue containing paraffin gas. The metal fraction of a wax-type solid body containing 48.6% by weight of oil has a specific weight (° API) 0.8853 *. Average molar weight (GPC) of the non-oil part 484 ,. 2.35% by weight of n-paraffins of 19-28. typically 22-28 carbon atoms and an average carbon amount of 24.9. It is believed that the composition of the non-oil part * 15 consists of iso- and cycloparaffins with 23-39 carbon atoms. Heavy aromatic naphtha (HAN). It is a solvent for additive mixers and typically has an aniline point at 24.6 ° C, specific gravity (° API) 0.933, boiling point 179-235 ° C and consists of 4 wt% paraffins, 6.7 wt% naphthenes , 87.3% by weight of aromatics, eg, polyalkyl aromatics, and 2.0% by weight of olefins. 25 The hydrocarbon polymer B7 consists of an oil concentrate as solvent containing about 5% ethylene propylene copolymer, which contains about 44% by weight ethylene and about 56% by weight propylene, with a thickening efficiency (TE) of 5. is the ratio of the percentage by weight of polyisobutylene (molar mass according to Standinger 2000) required to concentrate the reference oil to a viscosity of 1.24-10 · Pa.S. at 117 ° C, to the percentage by weight of ethylene-propylene copolymer required to concentrate the reference oil to the same viscosity. The reference oil is LP Solvent 40 150N oil, which is a solvent refined greasy hydrocarbon oil with a low liquid point ( Midcontien / t), characterized by a viscosity of 150-160 SUS at a temperature of 36 ° C and a viscosity index of 105, and a liquidity temperature of about -17.8 ° C. Taking the TE 5 value as a basis, the numerical average molecular weight of the ethylene-propylene copolymer is estimated as being at least 100,000. The B8 hydrocarbon polymer is a polymer containing about 44% of ethylene and about 56% of propylene with a compaction efficiency of 1.4 and a number average molecular weight of 17,000-20,000 and is used as a solution in an oil at a concentration of 13.6% by weight. B9 hydrocarbon polymer is a copolymer containing about 67% by weight of ethylene and about 23% by weight of propylene with an effective It has a concentration of about 2.8 and a number average time weight of about 55,000 and is used as an oil solution at a concentration of 6.9% by weight. The hydrocarbon polymer B10 is a concentrate in oil containing about 3.4% by weight of the hydrocarbon polymer B8 and 4.0% by weight of the hydrocarbon polymer B10.128 453 17 The hydrocarbon polymer Bil is a copolymer of β-ethylene with propylene containing approximately 44% ethylene and about 56% propylene with a concentration efficiency of about 2.8 and a number-average molecular weight of about 60,000-65,000 and is used as an oil solution with a concentration of 8.3% by weight. B12 hydrocarbon polymer is a polyisobuty. Len with a molar mass according to Standinger of about 10500 and a concentration efficiency of 0.6, and is used as a solution in an oil at a concentration of 35% by weight. All of the above ethylene propylene copolymers are prepared by the Ziegler-Natta synthesis route and have a weight ratio Average molecular weight to number average molecular weight, less than 4. Membrane osmometry is used to determine the molecular weight of these essentially linear polymers. oil is added to either 2000 ppm (parts per million) by weight, based on the weight of the fuel oil, or 1200 ppm to 20 ppm of a base additive blend of ethylene vinyl acetate, methyl oil and diamide, followed by the addition of the various the amounts of the abovementioned hydrocarbon polymers B6-B12. The blends obtained are tested by the low temperature flow test (LTFT) which is carried out as follows. 200 cm * of oil with the addition of a mixture is cooled from room temperature to a temperature of -1.1 ° C, then at a rate of 1 ° C per hour to a temperature of -17.8 ° C, then passed through a sieve with a mesh size 17 um sieve at a pressure of 152.4 mm Hg. The time (in seconds) for the sample to pass through the sieve and the amount of sample collected (in ml) are measured. If the sample passes through the sieve in less than 60 seconds, the test is considered to pass (P), if it passes through the sieve in less than 60 seconds. , it is considered that the attempt failed (F). The samples tested and the results obtained are given in the following Table 8. Table 8 1] Test 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 Addition of ppm 2000 BAP 3000 BAP + 400 B7 2000 BAP + 400 B8 1200 BAP 1200 BAP + 400 B7 1200 BAP + 400 B8 1 2000 BAP + 400 B9 1200 BAP + 400 B10 1200 BAP + 400 Bil 1200 BAP + 400 B12 1200 BAP + 400 B13 1200 BAP + 25 Bil 1200 BAP + 25 B13 800 A2 400 C4 400 B7 500 A2 250 C4 400 B7 500 A2 400 B7 800 micro-crystalline paraffin 400 B7 LTFT at temperature - Time in seconds 36.7 33.7 32.7 and 47 , 0 30.1 29.8 60.0 148.0 56.9 35.8 35.6 36.8 60.0 100.0 60.0 66.9 46.5 39.2 60.0 60.0 P / FPPPPPPFFPPPPFFFFPPFF -17.8 ° C Collected quantity (ml) 195 195 195 195 195 195 135 195 195 195 200 200 145 195 170 195 190 195 0 0 Percent improvement over BAP 8% 12% - 56% 51% - 68% - 18% 31% 32% 27% - 56% - 30% - 112 * 45? The judgments of tests 2 and * shown in Table 9 show that the filtered copolymers reduce the transitions, the bc samples are% sHo and the percentage improvement over baseline asphalt additive (BAP) is 9% and 12%. in the trial * reduces ¦i * itosfr basic} additive blends will give 1209 ppm. The sampling and 9 copolymers B7 and B8 with low ethylene content caused a significant reduction in the speed of fuel transfer by 2 additives * a fine sieve. Trial 7 has shown that a world of high-Eelylene B9 has a reciprocally negative velvity as demonstrated in the two LTFTi trials, resulting in an increase in the fuel flow time through the sieves. Test 9 shows similar results. Test 9 shows another example of using a copolymer with low ethylene contents to increase the flow rate through the screen. Trials 19 and 11 demonstrate the performance of polyisobutylene. In tests 12 and 13, the amounts of the polymer concentrate are reduced to 25 ppm, which, based on the active ingredient, is in fact only adding 3 ppm of this ingredient. In this case, the addition of a small amount of polymer causes an increase in the flow time through the filter and the failure of the test shows that the test mixture does not have the necessary ammonia to obtain positive results. Test 14 uses the above-mentioned A2 oil concentrate at a concentration of 860 ppm. and an addition of C4 at a concentration of 400 ppm, and an oil concentrate of B7 hydrocarbon polymer at a concentration of 400 ppm. Test 15 is carried out by mixing the same ingredients in different proportions. In Test 16 only diamide and a hydrocarbon polymer were used, in Run 17 flow-enhancing additive A2 and hydrocarbon polymer B7, and in Test 18 - 800 parts of microcrystalline paraffin in the form of a metallic oil fraction. All B7 hydrocarbon polymers - Bile in Table 9 is used in the form of concentrates, for example, in Test 2, polyether B7 is used at 400 ppm, or in the form of an actual copolymer at 20 ppm. Generally, as useful and particularly preferred components of the class Lubricant oil viscosity index improvers include hydrocarbon polymers with a number average molecular weight of 19 * -10 *, such as additives BI-B4 and B7-B13. Patent claims 1. Fuel additive containing copolymer 4-2 * molar parts of ethylene and 1 part of an unsaturated ester of the general formula RiR ^ C = CHB * where Rx represents a methyl group or a hydrogen atom, Rg represents a group of the formula -COOR4 or -OOCR * in which the formula R * represents an alkyl group of 1-28 carbon atoms, and R, represents a hydrogen atom or a group of the formula —COOR 4, and a copolymer of ethylene and propylene or isobutylene with a molecular weight of 10,000-100,000, characterized in that it contains an oil-soluble nitrogen compound with a total carbon number of 30-300, having at least one straight-chain alkyl segment of 8-40 carbon atoms, and being an amine salt and / or a hydrocarbon amide of a carbophenyl acid or its anhydride of 1-4 carbonyl groups, where, based on 1 part by weight of ethylene-ester copolymer, the blend contains 0.1-10 parts by weight of ethylene-propylene or isobutylene copolymer and 0.1-10 parts by weight of an oil-soluble nitrogen compound. 2. Additive according to claim The process of claim 1, wherein the nitrogen containing compound is a derivative of phthalic acid or phthalic anhydride, in which both carboxyl groups have reacted with a secondary alkyl monoamide having alkyl groups essentially of 14 to 28 carbon atoms. 3. Fuel additive according to claim The method of claim 1, characterized in that it contains a hydrocarbon solvent in an amount of 30-80% by weight. Koszalin A101 80 A-4 Price PLN 100 PL

Claims (3)

Claims 1. A fuel additive containing a copolymer of 4-2 * mole parts of ethylene and 1 part of an unsaturated ester of the general formula RiR ^ C = CHB * where Rx is a methyl group or a hydrogen atom, Rg is a group of the formula -COOR4 or -OOCR * wherein R * represents an alkyl group of 1-28 carbon atoms, and R, represents a hydrogen atom or a group of the formula —COOR 4, and a copolymer of ethylene and propylene or isobutylene with a molecular weight of 10,000-100,000, characterized by that it contains an oil-soluble nitrogen compound with a total carbon number of 30-300, having at least one straight-chain alkyl segment of 8-40 carbon atoms, and being an amine salt and / or a hydrocarbon amide of carbophenyl acid or its anhydride with 1-4 carbonyl groups, where, based on 1 part by weight of ethylene-ester copolymer, the mixture contains 0.1-10 parts by weight of ethylene-propylene or isobutylene copolymer and 0.1-10 parts by weight of oil-solublenitrogen compound. 2. Additive according to claim The process of claim 1, wherein the nitrogen containing compound is a derivative of phthalic acid or phthalic anhydride, in which both carboxyl groups have reacted with a secondary alkyl monoamide having alkyl groups essentially of 14 to 28 carbon atoms. 3. Fuel additive according to claim The process of claim 1, wherein the hydrocarbon solvent is present in an amount of 30-80% by weight. PZGraf. Koszalin A101 80 A-4 Price PLN 100 PL